Sodium hydride → N-(2-methyl-3-nitrophenylmethyl)iminodicarboxylic acid di-t-butyl ester

HRID 1861925Notes

Reaction equation

HRID 1861925 reaction equation
[CH3:1][C:2]1[C:9]([N+:10]([O-:12])=[O:11])=[CH:8][CH:7]=[CH:6][C:3]=1[CH2:4]Cl.[NH:13]([C:21]([O:23][C:24]([CH3:27])([CH3:26])[CH3:25])=[O:22])[C:14]([O:16][C:17]([CH3:20])([CH3:19])[CH3:18])=[O:15].[H-].[Na+]>CN(C)C=O>[C:24]([O:23][C:21]([N:13]([C:14]([O:16][C:17]([CH3:20])([CH3:19])[CH3:18])=[O:15])[CH2:4][C:3]1[CH:6]=[CH:7][CH:8]=[C:9]([N+:10]([O-:12])=[O:11])[C:2]=1[CH3:1])=[O:22])([CH3:27])([CH3:26])[CH3:25]

Participants

5

Reactant 3

HCID 24758Sodium hydrideHCID 108947alpha-Chloro-2-methyl-3-nitrotolueneHCID 279800Di-tert-butyl Iminodicarboxylate

Product 1

HCID 54468410N-(2-methyl-3-nitrophenylmethyl)iminodicarboxylic acid di-t-butyl esterYield 96%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent2×

Procedure

A solution of 2-methyl-3-nitrobenzyl chloride (1.07 g) in dimethylformamide (30 ml) was added dropwise to a solution of di-t-butyl iminodicarboxylate (1.38 g) and sodium hydride (content, 60%; 0.30 g) in dimethylformamide (30 ml) at 0° C. Following 1-h stirring at room temperature, the temperature of the mixture was raised to 80° C. and stirred for 1 h. The reaction mixture was concentrated under reduced pressure, water was added to the residue, and the mixture was extracted with ethyl acetate. The organic layer was washed with a saturated aqueous sodium chloride solution, dried with anhydrous sodium sulfate and concentrated under reduced pressure. The resulting residue was purified by silica gel column chromatography (eluent, n-hexane:ethyl acetate=10:1) to give 1.49 g of the titled compound (yield, 96%).

Workup

  1. temperaturethe temperature of the mixture was raised to 80° C.
  2. stirringstirred for 1 h
  3. concentrationThe reaction mixture was concentrated under reduced pressure, water
  4. additionwas added to the residue
  5. extractionthe mixture was extracted with ethyl acetate
  6. washThe organic layer was washed with a saturated aqueous sodium chloride solution
  7. dry with materialdried with anhydrous sodium sulfate
  8. concentrationconcentrated under reduced pressure
  9. customThe resulting residue was purified by silica gel column chromatography (eluent, n-hexane:ethyl acetate=10:1)

Sources & evidence

ORD record
ord-eff9a61483d9414b8c06d252beccb90a
Source dataset
uspto-grants-2003_03
Patent number
US06534546B1

Reaction notes

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